JP5089015B2 - Rotaxane having a plurality of ring components, production method thereof, and cross-linking agent comprising the same - Google Patents
Rotaxane having a plurality of ring components, production method thereof, and cross-linking agent comprising the same Download PDFInfo
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- 239000003431 cross linking reagent Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 14
- 150000003983 crown ethers Chemical class 0.000 claims description 35
- 238000004132 cross linking Methods 0.000 claims description 31
- 125000000524 functional group Chemical group 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920006037 cross link polymer Polymers 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 22
- -1 3,5-di-tert-butylphenyl group Chemical group 0.000 description 21
- 239000007787 solid Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 125000003396 thiol group Chemical group [H]S* 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 0 **(*)**[N+](C1C*C1)[O-] Chemical compound **(*)**[N+](C1C*C1)[O-] 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 3
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- WIXDSJRJFDWTNY-UHFFFAOYSA-N 1,3-ditert-butyl-5-methylbenzene Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 WIXDSJRJFDWTNY-UHFFFAOYSA-N 0.000 description 2
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 2
- NJYSMUZHMILTRA-UHFFFAOYSA-N 2,5,8,11,14,17,20,23-octaoxabicyclo[22.4.0]octacosa-1(28),24,26-triene Chemical compound O1CCOCCOCCOCCOCCOCCOCCOC2=CC=CC=C21 NJYSMUZHMILTRA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- QMLGNDFKJAFKGZ-UHFFFAOYSA-N dicyclohexano-24-crown-8 Chemical compound O1CCOCCOCCOC2CCCCC2OCCOCCOCCOC2CCCCC21 QMLGNDFKJAFKGZ-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JYWKEVKEKOTYEX-UHFFFAOYSA-N 2,6-dibromo-4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=C(Br)C(=O)C(Br)=C1 JYWKEVKEKOTYEX-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NCTSLPBQVXUAHR-UHFFFAOYSA-N 3,5-ditert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1 NCTSLPBQVXUAHR-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- WGSDZBKYQFGDHO-UHFFFAOYSA-N [fluoro(fluorooxy)boranyl] hypofluorite Chemical compound FOB(F)OF WGSDZBKYQFGDHO-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Description
本発明は、少なくとも一個の官能基を有するクラウンエーテル分子を少なくとも二個輪成分として有するロタキサン、該ロタキサンからなる架橋剤、該ロタキサンの製造方法、該ロタキサンを利用した架橋方法、および該架橋方法により架橋して得られた架橋ポリマーに関する。 The present invention relates to a rotaxane having a crown ether molecule having at least one functional group as at least two ring components, a crosslinking agent comprising the rotaxane, a method for producing the rotaxane, a crosslinking method using the rotaxane, and the crosslinking method. The present invention relates to a crosslinked polymer obtained by crosslinking.
物理架橋または化学架橋によって架橋体が作られ、ゲル、ビーズなどとして利用されている。物理架橋体は時間の経過や条件によって性質が変化しやすいという欠点がある。一方、化学架橋体では架橋点が化学結合で固定されているため、架橋体が引っ張られたときに架橋点間の長さが短い結合にはより大きな負荷がかかりやすい。結果として、機械的強度に優れた架橋体が得にくい。 A crosslinked product is produced by physical crosslinking or chemical crosslinking, and is used as a gel, a bead, or the like. The physical cross-linked product has a drawback that its properties are likely to change over time and conditions. On the other hand, since the crosslinking points are fixed by chemical bonds in the chemically crosslinked body, a larger load is likely to be applied to the bonds having a short length between the crosslinking points when the crosslinked body is pulled. As a result, it is difficult to obtain a crosslinked product having excellent mechanical strength.
これに対し、架橋点が自由に移動できる架橋剤、すなわち、いわゆる「トポロジカル架橋剤」を用いれば、架橋点が移動できるために負荷が分子鎖全体にまんべんなくかかり、機械的強度に優れた架橋体を得ることができる。ロタキサンは軸成分と輪成分とからなり、輪成分が軸成分上を自由に移動できるので、トポロジカル架橋剤としての利用が試みられている。例えば、シクロデキストリンを輪成分として有するロタキサンを用いたトポロジカル架橋剤が知られている（特許文献１）。 On the other hand, if a cross-linking agent that can freely move cross-linking points, that is, a so-called “topological cross-linking agent” is used, the cross-linking points can be moved, so the load is evenly applied to the entire molecular chain, and the cross-linked product has excellent mechanical strength. Can be obtained. Rotaxane is composed of a shaft component and a ring component, and the ring component can freely move on the shaft component. Therefore, use as a topological crosslinking agent has been attempted. For example, a topological crosslinking agent using a rotaxane having cyclodextrin as a ring component is known (Patent Document 1).
また、−Ｎ＋Ｈ２−で表されるアンモニウム基を鎖中に一個有し、両末端にヒドロキシル基を有する直鎖状化合物と、官能基を有さないクラウンエーテルとを反応させてクラウンエーテルと前記アンモニウム基との相互吸引作用による両者の会合体を生成させ、次に、該会合体中の直鎖状化合物の両末端ヒドロキシル基を嵩高い基を持つ酸無水物でエンドキャップすることにより、輪成分として官能基を有さないクラウンエーテルを一個有するロタキサンを合成することが知られている（非特許文献１）。また、−Ｎ＋Ｈ２−で表されるアンモニウム基を鎖中に四個有し、両末端にヒドロキシル基を有する直鎖状化合物と、官能基を有さないクラウンエーテルとから、非特許文献１と同様にして、四個のクラウンエーテル分子を有する会合体を得、次に、エンドキャップすることにより、輪成分として官能基を有さないクラウンエーテルを四個有するロタキサンを合成することが知られている（非特許文献２）。 In addition, a linear compound having one ammonium group represented by -N + H 2- in the chain and having hydroxyl groups at both ends and a crown ether having no functional group are reacted to form a crown ether And the ammonium group by mutual suction action, and then end-capping both terminal hydroxyl groups of the linear compound in the aggregate with a bulky acid anhydride. It is known to synthesize a rotaxane having one crown ether having no functional group as a ring component (Non-patent Document 1). Further, -N + H 2 - has four with ammonium groups represented in the chain, from a straight-chain compound having a hydroxyl group at both ends, a crown ether having no functional group, non-patent literature It is known that a rotaxane having four crown ethers having no functional group as a ring component is synthesized by obtaining an aggregate having four crown ether molecules and then end-capping in the same manner as in 1. (Non-Patent Document 2).
しかし、これまでに合成されているロタキサン架橋剤には、用いることのできるポリマーが限られていること、合成ステップが長いこと、輪成分の個数が制御できないので得られる架橋体の性質を制御できないことなどの問題があった。 However, the rotaxane crosslinking agents synthesized so far are limited in the polymers that can be used, the synthesis step is long, and the number of ring components cannot be controlled, so the properties of the resulting crosslinked product cannot be controlled. There was a problem such as.
本発明の目的は、輪成分の個数を制御可能なロタキサンを提供することである。 An object of the present invention is to provide a rotaxane capable of controlling the number of ring components.
また、本発明の目的は、該ロタキサンを利用して、架橋点が自由に移動する架橋剤、すなわち、いわゆるトポロジカル架橋剤を提供することである。 Another object of the present invention is to provide a cross-linking agent in which a cross-linking point moves freely using the rotaxane, that is, a so-called topological cross-linking agent.
更に、本発明の目的は、該ロタキサンの製造方法、該ロタキサンを利用した架橋方法、および該架橋方法により架橋して得られた架橋ポリマーを提供することである。 Furthermore, the object of the present invention is to provide a method for producing the rotaxane, a crosslinking method using the rotaxane, and a crosslinked polymer obtained by crosslinking by the crosslinking method.
本発明は、上記の課題を解決する手段として、
一般式Ｒ１−Ｒ２−Ｒ１（式中、Ｒ１は独立に、エンドキャップとして働く一価の基であり、Ｒ２は直鎖状の二価の基からなる直鎖部である。）で表される軸成分と、
該軸成分の直鎖部を周回する状態で保持される、少なくとも一個の官能基を有するクラウンエーテル分子少なくとも二個からなる輪成分と、
を有するロタキサン、および該ロタキサンからなる架橋剤を提供する。
As a means for solving the above problems, the present invention provides:
General formula R 1 -R 2 -R 1 (wherein R 1 is independently a monovalent group that acts as an end cap, and R 2 is a linear part composed of a linear divalent group. ) And the axis component represented by
A ring component composed of at least two crown ether molecules having at least one functional group, which is held in a state where it circulates around the linear portion of the shaft component;
And a crosslinking agent comprising the rotaxane.
更に、本発明は、前記ロタキサンを製造する方法であって、
（１）少なくとも一個の官能基を有するクラウンエーテルと、一般式(i):
Ｒ１−Ｒ２ａ−Ｙ (i)
（式中、Ｒ１は上記の通りであり、Ｒ２ａは、前記クラウンエーテルと相互吸引作用を行う基または原子Ｘを少なくとも１個有する二価の基であり、Ｙは反応性基である。）
で表される化合物とを反応させることにより、前記一般式(i)の化合物が該クラウンエーテルの環内に相互吸引作用により保持されてなる会合体を得、
（２）該会合体を、一般式(ii):
Ｚ−Ｒ２ｂ−Ｚ (ii)
（式中、Ｒ２ｂは直鎖状の二価の基であり、Ｚは前記Ｙと反応する反応性基である。）
で表される化合物と反応させることにより、一般式(iii):
Ｒ１−Ｒ２’−Ｒ１ (iii)
（式中、Ｒ１は上記の通りであり、Ｒ２'は前記Ｘを少なくとも２個有する直鎖状の二価の基である。）
で表され、前記クラウンエーテルが前記Ｘに前記相互吸引作用により保持されている化合物を得、
（３）前記Ｘを、前記相互吸引作用を行わない基または原子に変換すること
を含む、上記ロタキサンの製造方法を提供する。
Furthermore, the present invention is a method for producing the rotaxane,
(1) a crown ether having at least one functional group and a general formula (i):
R 1 -R 2a -Y (i)
(Wherein R 1 is as described above, R 2a is a group capable of mutual attraction with the crown ether or a divalent group having at least one atom X, and Y is a reactive group). )
To obtain an aggregate in which the compound of the general formula (i) is held in the ring of the crown ether by a mutual suction action.
(2) The aggregate is represented by the general formula (ii):
Z-R 2b -Z (ii)
(In the formula, R 2b is a linear divalent group, and Z is a reactive group that reacts with Y.)
By reacting with a compound represented by the general formula (iii):
R 1 —R 2 ′ —R 1 (iii)
(In the formula, R 1 is as described above, and R 2 ′ is a linear divalent group having at least two Xs.)
A compound in which the crown ether is retained in X by the mutual suction action is obtained,
(3) Provided is a method for producing the rotaxane, which comprises converting the X into a group or an atom that does not perform the mutual attractive action.
また、本発明は、前記ロタキサンにより、該ロタキサンが有する官能基と反応する反応性基を一分子中に少なくとも２個有するポリマー成分を架橋させることからなるポリマー成分の架橋方法、および該架橋方法により架橋して得られた架橋ポリマーを提供する。 In addition, the present invention provides a method for crosslinking a polymer component comprising cross-linking a polymer component having at least two reactive groups in one molecule that reacts with a functional group of the rotaxane with the rotaxane, and the crosslinking method. A crosslinked polymer obtained by crosslinking is provided.
本発明のロタキサンはトポロジカル架橋剤として用いることができる。また、本発明の製造方法によれば、短いステップで効率よく、ロタキサンを合成することができる。さらに、本発明の製造方法によれば、ロタキサンの輪成分の個数を制御することができるので、得られる架橋体の性質を制御することもできる。本発明によるトポロジカル架橋剤および架橋方法は特定のポリマーに限らず用いることができる。このように、本発明は、強度が高い新素材、更には、ゲルなどのように高機能性の新素材の開発への利用が期待できる。 The rotaxane of the present invention can be used as a topological crosslinking agent. Moreover, according to the production method of the present invention, rotaxane can be efficiently synthesized in a short step. Furthermore, according to the production method of the present invention, the number of ring components of rotaxane can be controlled, so that the properties of the obtained crosslinked product can also be controlled. The topological crosslinking agent and the crosslinking method according to the present invention can be used without being limited to a specific polymer. As described above, the present invention can be expected to be used for the development of new materials with high strength, and further, new materials with high functionality such as gel.
以下、本発明について更に詳しく説明する。なお、本明細書において、「Ac」はアセチル基を、「Me」はメチル基を、「tBu」はtert−ブチル基を意味する。 Hereinafter, the present invention will be described in more detail. In this specification, “Ac” means an acetyl group, “Me” means a methyl group, and “ t Bu” means a tert-butyl group.
［軸成分］
本発明のロタキサンの軸成分は、一般式Ｒ１−Ｒ２−Ｒ１（式中、Ｒ１は独立に、エンドキャップとして働く一価の基であり、Ｒ２は直鎖状の二価の基からなる直鎖部である。）で表される。
[Axis component]
The axial component of the rotaxane of the present invention has the general formula R 1 -R 2 -R 1 (wherein R 1 is independently a monovalent group acting as an end cap, and R 2 is a linear divalent group) It is a straight chain part composed of a group.
前記Ｒ１は、本発明のロタキサンの輪成分を、前記軸成分の直鎖部を周回する状態で保持させることができる限り、特に制限されない。例えば、前記輪成分を構成するクラウンエーテル分子の環を通り抜けることができない程度に嵩高い一価の基が挙げられる。その具体例としては、３，５−ジ−ｔｅｒｔ−ブチルフェニル基、３，５−ジメチルフェニル基、２，６-ジメチルフェニル基、３，５-ジニトロフェニル基、４−tert-ブチルフェニル基、２，４，６-トリメチルフェニル基、tert-ブチル基、トリチル基などが挙げられ、中でも３，５−ジ−ｔｅｒｔ−ブチルフェニル基、３，５−ジメチルフェニル基、４−tert-ブチルフェニル基が好ましい。 The R 1 is not particularly limited as long as the ring component of the rotaxane of the present invention can be held in a state of circling the linear portion of the shaft component. For example, a monovalent group that is bulky to such an extent that it cannot pass through the ring of the crown ether molecule constituting the ring component can be mentioned. Specific examples thereof include 3,5-di-tert-butylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dinitrophenyl group, 4-tert-butylphenyl group, 2,4,6-trimethylphenyl group, tert-butyl group, trityl group and the like are mentioned, among which 3,5-di-tert-butylphenyl group, 3,5-dimethylphenyl group, 4-tert-butylphenyl group Is preferred.
前記Ｒ２は特に制限されないが、高分子鎖であることが好ましい。Ｒ２としては、例えば、下記の基が挙げられる。 The R 2 is not particularly limited, but is preferably a polymer chain. Examples of R 2 include the following groups.
［輪成分］
本発明のロタキサンの輪成分は、前記軸成分の直鎖部を周回する状態で保持される、少なくとも一個の官能基を有するクラウンエーテル分子少なくとも二個からなる。該輪成分は該軸成分の直鎖部上を自由に動くことができる。一方、軸成分の両末端に存在するエンドキャップ（基Ｒ１）により直鎖部（基Ｒ２）上に保持される。
[Round component]
The ring component of the rotaxane of the present invention is composed of at least two crown ether molecules having at least one functional group, which are held in a state of circling the straight chain portion of the shaft component. The ring component can move freely on the linear part of the shaft component. On the other hand, it is held on the straight chain part (group R 2 ) by end caps (group R 1 ) present at both ends of the shaft component.
前記輪成分を構成するクラウンエーテル分子の環の員数は好ましくは２２〜３０、より好ましくは２４〜２８である。該クラウンエーテル分子の環には炭素原子および酸素原子だけでなく、窒素原子、硫黄原子などが存在していてもよい。該クラウンエーテル分子としては、例えば、ジベンゾ−２４−クラウン−８、２４-クラウン-８、ベンゾ-２４-クラウン-８、ビス（ビナフチル）-２８-クラウン-８、ビス（ビフェニル）-２８-クラウン-８、ジシクロヘキシル-２４-クラウン-８、 ベンゾ/ビナフチル-２４-クラウン-８などが挙げられ、中でもジベンゾ−２４−クラウン−８、２４-クラウン-８、ベンゾ-２４-クラウン-８、ジシクロヘキシル-２４-クラウン-８が好ましい。 The number of ring members of the crown ether molecule constituting the ring component is preferably 22-30, more preferably 24-28. The ring of the crown ether molecule may contain not only a carbon atom and an oxygen atom but also a nitrogen atom, a sulfur atom and the like. Examples of the crown ether molecule include dibenzo-24-crown-8, 24-crown-8, benzo-24-crown-8, bis (binaphthyl) -28-crown-8, and bis (biphenyl) -28-crown. -8, dicyclohexyl-24-crown-8, benzo / binaphthyl-24-crown-8, etc., among which dibenzo-24-crown-8, 24-crown-8, benzo-24-crown-8, dicyclohexyl- 24-Crown-8 is preferred.
前記官能基としては、例えば、メルカプトメチル基、メルカプト基、アミノメチル基、アミノ基、水酸基、ヒドロキシルメチル基、カルボキシル基、カルボキシルメチル基、ハロゲノメチル基、ハロゲン基などが挙げられ、中でもメルカプトメチル基、メルカプト基、アミノメチル基、アミノ基が好ましい。クラウンエーテル１個あたりの官能基の数は、少なくとも１である限り、かつ、構造上可能である限り特に制限されないが、通常１〜８の範囲で容易に制御することができる。ロタキサン１分子当りのクラウンエーテル分子の数は少なくとも２個であり、２〜１６の範囲で制御することができる。 Examples of the functional group include a mercaptomethyl group, a mercapto group, an aminomethyl group, an amino group, a hydroxyl group, a hydroxylmethyl group, a carboxyl group, a carboxylmethyl group, a halogenomethyl group, and a halogen group. , A mercapto group, an aminomethyl group, and an amino group are preferable. The number of functional groups per crown ether is not particularly limited as long as it is at least 1 and is structurally possible, but can usually be easily controlled in the range of 1-8. The number of crown ether molecules per rotaxane molecule is at least 2 and can be controlled in the range of 2-16.
少なくとも一個の官能基を有するクラウンエーテル分子の具体例としては、下記の化合物が挙げられる。 Specific examples of the crown ether molecule having at least one functional group include the following compounds.
［架橋剤］
本発明のロタキサンは、一個の軸成分と少なくとも二個の輪成分とからなる。各輪成分上に少なくとも一個の官能基を有するので、本発明のロタキサンは全体として二個以上の官能基を有し、架橋剤として用いることができる。架橋点となる官能基の数は、クラウンエーテル一個当りの官能基数および／またはロタキサン１分子当りのクラウンエーテル分子数を調節することによって所望のように変えることができる。架橋剤としてどのような挙動、どの程度の架橋点数が求められるか、個別の要求に応じて制御することができる。通常は、クラウンエーテル一分子当り官能基数が１〜８（好ましくは２〜８）で、ロタキサン全体としては官能基数が２〜１６（好ましくは４〜１６）でよい。なお、各クラウンエーテル分子上の官能基数は同じでも異なってもよい。
[Crosslinking agent]
The rotaxane of the present invention comprises one axial component and at least two ring components. Since at least one functional group is present on each ring component, the rotaxane of the present invention has two or more functional groups as a whole and can be used as a crosslinking agent. The number of functional groups serving as crosslinking points can be varied as desired by adjusting the number of functional groups per crown ether and / or the number of crown ether molecules per rotaxane molecule. It is possible to control according to individual requirements what behavior and how many crosslinking points are required as a crosslinking agent. Usually, the number of functional groups per molecule of crown ether is 1 to 8 (preferably 2 to 8), and the whole rotaxane may have 2 to 16 functional groups (preferably 4 to 16). The number of functional groups on each crown ether molecule may be the same or different.
前記輪成分は前記軸成分上を自由に移動することができるので、本発明のロタキサンを架橋剤として用いた場合、架橋点となる輪成分と軸成分との交点は軸成分上を自由に移動することができる。すなわち、本発明のロタキサンはトポロジカル架橋剤として用いることができる。 Since the ring component can move freely on the shaft component, when the rotaxane of the present invention is used as a cross-linking agent, the intersection of the ring component and the shaft component that becomes a cross-linking point moves freely on the shaft component. can do. That is, the rotaxane of the present invention can be used as a topological crosslinking agent.
［製造方法］
本発明の製造方法では、工程（１）において、少なくとも一個の官能基を有するクラウンエーテルと、一般式(i):
Ｒ１−Ｒ２ａ−Ｙ (i)
（式中、Ｒ１は上記の通りであり、Ｒ２ａは、前記クラウンエーテルと相互吸引作用を行う基または原子Ｘを少なくとも１個有する二価の基であり、Ｙは反応性基である。）
で表される化合物とを反応させることにより、前記一般式(i)の化合物が該クラウンエーテルの環内に相互吸引作用により保持されてなる会合体を得る。前記Ｘの数を変えることにより、所望の個数のクラウンエーテル分子を前記会合体中に保持させることができ、最終的には本発明のロタキサンに含まれる輪成分の個数を制御することができる。
[Production method]
In the production method of the present invention, in step (1), a crown ether having at least one functional group and a general formula (i):
R 1 -R 2a -Y (i)
(Wherein R 1 is as described above, R 2a is a group capable of mutual attraction with the crown ether or a divalent group having at least one atom X, and Y is a reactive group). )
Is reacted with a compound represented by the formula (i) to obtain an aggregate in which the compound of the general formula (i) is held in the ring of the crown ether by a mutual suction action. By changing the number of X, a desired number of crown ether molecules can be retained in the aggregate, and finally the number of ring components contained in the rotaxane of the present invention can be controlled.
前記Ｘとしては、例えば、−Ｎ＋Ｈ２−で表される基、−Ｎ＋Ｈ（Ｍｅ）−で表される基などが挙げられ、中でも−Ｎ＋Ｈ２−で表される基が好ましい。 Examples of X include a group represented by -N + H 2- , a group represented by -N + H (Me)-, and the like, and among them, a group represented by -N + H 2- preferable.
前記Ｒ２ａとしては、例えば、下記の基が挙げられる。 Examples of R 2a include the following groups.
前記Ｙは、後述する反応性基Ｚと反応する反応性基である限り特に制限されない。前記Ｙとしては、例えば、水酸基、メルカプト基、カルボキシル基、イソシアナート基、アミノ基、トリチルオキシ基、トリチルチオ基、イソチオシアナート基などが挙げられ、中でも水酸基、メルカプト基、アミノ基が好ましい。 Y is not particularly limited as long as it is a reactive group that reacts with a reactive group Z described later. Examples of Y include a hydroxyl group, a mercapto group, a carboxyl group, an isocyanate group, an amino group, a trityloxy group, a tritylthio group, and an isothiocyanate group. Of these, a hydroxyl group, a mercapto group, and an amino group are preferable.
前記会合体の形成は、前記クラウンエーテルと一般式(i)で表される化合物とを溶液中で混合することで行われる。溶媒は特に制限されないが、例えば、クロロホルム、ベンゼン、テトラヒドロフラン、アセトニトリル、塩化メチレン、トルエンなどを用いることができる。 The association is formed by mixing the crown ether and the compound represented by the general formula (i) in a solution. The solvent is not particularly limited, and for example, chloroform, benzene, tetrahydrofuran, acetonitrile, methylene chloride, toluene and the like can be used.
次に、本発明の製造方法の工程（２）では、前記会合体を、一般式(ii):
Ｚ−Ｒ２ｂ−Ｚ (ii)
（式中、Ｒ２ｂは直鎖状の二価の基であり、Ｚは前記Ｙと反応する反応性基である。）
で表される化合物と反応させることにより、一般式(iii):
Ｒ１−Ｒ２’−Ｒ１ (iii)
（式中、Ｒ１は上記の通りであり、Ｒ２'は前記Ｘを少なくとも２個有する直鎖状の二価の基である。）
で表され、前記クラウンエーテルが前記Ｘに前記相互吸引作用により保持されている化合物を得る。
Next, in the step (2) of the production method of the present invention, the aggregate is represented by the general formula (ii):
Z-R 2b -Z (ii)
(In the formula, R 2b is a linear divalent group, and Z is a reactive group that reacts with Y.)
By reacting with a compound represented by the general formula (iii):
R 1 —R 2 ′ —R 1 (iii)
(In the formula, R 1 is as described above, and R 2 ′ is a linear divalent group having at least two Xs.)
And a compound in which the crown ether is held in X by the mutual suction action is obtained.
前記Ｒ２ｂは特に制限されないが、高分子鎖であることが好ましい。Ｒ２ｂとしては、例えば、下記の基が挙げられる。 The R 2b is not particularly limited, but is preferably a polymer chain. Examples of R 2b include the following groups.
前記Ｚは、前記Ｙと反応する反応性基である限り特に制限されない。前記ＹとＺとの組み合わせとしては、例えば、水酸基とイソシアナート基、水酸基とカルボキシル基、メルカプト基とメルカプト基、カルボキシル基とアミノ基、水酸基とイソチオシアナート基、アミノ基とイソシアナート基、メルカプト基とイソシアナート基、メルカプト基とカルボキシル基などが挙げられ、中でも水酸基とイソシアナート基、メルカプト基とイソシアナート基、アミノ基とイソシアナート基が好ましい。 Z is not particularly limited as long as it is a reactive group that reacts with Y. Examples of the combination of Y and Z include, for example, a hydroxyl group and an isocyanate group, a hydroxyl group and a carboxyl group, a mercapto group and a mercapto group, a carboxyl group and an amino group, a hydroxyl group and an isothiocyanate group, an amino group and an isocyanate group, and a mercapto group. Groups and isocyanate groups, mercapto groups and carboxyl groups, etc., among which hydroxyl groups and isocyanate groups, mercapto groups and isocyanate groups, amino groups and isocyanate groups are preferred.
前記会合体と一般式(ii)で表される化合物との反応は、前記Ｙと前記Ｚとを当業者に公知の方法で反応させることにより行うことができる。場合により、三級アミン、ジラウリン酸ジ-n-ブチルスズ、トリフロロボロン酸エーテル錯体などの触媒を添加してもよい。例えば、Ｙが水酸基、Ｚがイソシアナート基の場合には、前記会合体に一般式(ii)で表される化合物と触媒であるジラウリン酸ジ-n-ブチルスズとを添加することにより反応を行うことができる。反応温度は特に制限されないが、好ましくは室温である。通常、一晩、放置することで反応を十分に進行させることができる。反応は通常、溶液中で行われる。溶媒は特に制限されないが、例えば、クロロホルム、ベンゼン、テトラヒドロフラン、アセトニトリル、塩化メチレン、トルエンなどを用いることができる。 The reaction between the aggregate and the compound represented by the general formula (ii) can be performed by reacting the Y and the Z with a method known to those skilled in the art. In some cases, a catalyst such as a tertiary amine, di-n-butyltin dilaurate, or a trifluoroboronic acid ether complex may be added. For example, when Y is a hydroxyl group and Z is an isocyanate group, the reaction is performed by adding the compound represented by the general formula (ii) and di-n-butyltin dilaurate as a catalyst to the aggregate. be able to. The reaction temperature is not particularly limited but is preferably room temperature. Usually, the reaction can be allowed to proceed sufficiently by allowing it to stand overnight. The reaction is usually performed in solution. The solvent is not particularly limited, and for example, chloroform, benzene, tetrahydrofuran, acetonitrile, methylene chloride, toluene and the like can be used.
本発明の製造方法の工程（３）では、前記Ｘを、前記相互吸引作用を行わない基または原子に変換し、本発明のロタキサンを生成させる。この変換により、前記相互吸引作用は失われ、前記クラウンエーテルは前記Ｒ１の間の直鎖部上を自由に動くことができるようになる。 In step (3) of the production method of the present invention, the X is converted into a group or atom that does not perform the mutual attraction action to produce the rotaxane of the present invention. By this conversion, the mutual suction action is lost, and the crown ether can move freely on the linear part between the R 1 .
前記相互吸引作用を行わない基または原子としては、例えば、前記Ｘが−Ｎ＋Ｈ２−で表される基である場合には−ＮＡｃ−で表される基が挙げられる。 Examples of the group or atom that does not perform the mutual attractive action include a group represented by -NAc- when X is a group represented by -N + H 2- .
上記の変換は、当業者に公知の方法で行うことができる。例えば、前記Ｘが−Ｎ＋Ｈ２−で表される基である場合には、一般式(iii)で表される化合物をＤＭＦ中、トリエチルアミン存在下で無水酢酸と反応させることにより、前記Ｘを−ＮＡｃ−で表される基に変換することができる。 Said conversion can be performed by a method well-known to those skilled in the art. For example, when X is a group represented by -N + H 2- , the compound represented by the general formula (iii) is reacted with acetic anhydride in DMF in the presence of triethylamine, to thereby form the X Can be converted to a group represented by -NAc-.
生成したロタキサンの精製は、例えば、分取ゲル透過クロマトグラフィーなどの当業者に公知の方法で行うことができる。また、生成したロタキサンの同定は１Ｈ−ＮＭＲ、ＩＲスペクトル、元素分析などの当業者に公知の方法で行うことができる。 The produced rotaxane can be purified by methods known to those skilled in the art, such as preparative gel permeation chromatography. In addition, the produced rotaxane can be identified by methods known to those skilled in the art, such as 1 H-NMR, IR spectrum, and elemental analysis.
［架橋方法および架橋ポリマー］
本発明の架橋方法において、本発明のロタキサンにより架橋されるポリマー成分が有する少なくとも２個の反応性基は、該ロタキサンが有する官能基と反応する限り、特に制限されない。例えば、前記官能基がメルカプトメチル基である場合には、メルカプト基、イソシアナート基などが挙げられる。他の組み合わせとしては、例えば、ヒドロキシルメチル基とイソシアナート基やイソチオシアナート基、アミノ基とイソシアナート基やイソチオシアナート基、ヒドロキシル基とハロゲン化カルボニル基（−ＣＯＸ；Ｘはハロゲン）やケテン基などが挙げられる。
[Crosslinking method and crosslinked polymer]
In the crosslinking method of the present invention, at least two reactive groups of the polymer component crosslinked by the rotaxane of the present invention are not particularly limited as long as they react with the functional group of the rotaxane. For example, when the functional group is a mercaptomethyl group, examples thereof include a mercapto group and an isocyanate group. Other combinations include, for example, a hydroxylmethyl group and an isocyanate group or an isothiocyanate group, an amino group and an isocyanate group or an isothiocyanate group, a hydroxyl group and a carbonyl halide group (—COX; X is a halogen), or a ketene. Group and the like.
本発明の架橋方法を用いて前記ポリマー成分を架橋させることにより架橋ポリマーを得ることができる。 A crosslinked polymer can be obtained by crosslinking the polymer component using the crosslinking method of the present invention.
本発明の架橋剤を用いて架橋させるのに適したポリマーとしては、特に限定するものではないが、例えば、下記式で表されるポリマーが挙げられる。 Although it does not specifically limit as a polymer suitable for bridge | crosslinking using the crosslinking agent of this invention, For example, the polymer represented by a following formula is mentioned.
以下に、実施例および比較例を示し、本発明を具体的に説明するが、本発明はこれらの実施例に制限されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
［調製例１］ 二官能性クラウンエーテルの合成
アルゴン雰囲気下、ジベンゾ−２４−クラウン−８ 10.8g(24.1mmol)、ヘキサメチレンテトラミン14.0g(99.1mmol)をトリフルオロ酢酸50mLに溶解し、得られた溶液を80℃で一晩撹絆した。この溶液に水30mLを加え室温で2時間撹拌した後、クロロホルムを加えて油層を分離し、油層のクロロホルムを減圧留去した。残渣をシリカゲルカラムクロマトグラフィー（溶離液/クロロホルム→2%メタノール-クロロホルム）により精製し、白色固体として下記のジホルミル体10.5g(20.8mmol,86%)を得た。
[Preparation Example 1] Synthesis of bifunctional crown ether Dibenzo-24-crown-8 10.8 g (24.1 mmol) and hexamethylenetetramine 14.0 g (99.1 mmol) were dissolved in 50 mL of trifluoroacetic acid in an argon atmosphere. The solution was stirred at 80 ° C. overnight. After adding 30 mL of water to this solution and stirring at room temperature for 2 hours, chloroform was added to separate the oil layer, and chloroform in the oil layer was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent / chloroform → 2% methanol-chloroform) to obtain 10.5 g (20.8 mmol, 86%) of the following diformyl compound as a white solid.
上記のジホルミル体10.5g(20.8mmol)をTHF120mLに溶解した後、氷浴下、水素化アルミニウムリチウム3.95g(83.2mmol)を少しずつ加えて懸濁させ、一晩還流した。飽和硫酸ナトリウム水溶液で過剰な水素化アルミニウムリチウムを分解し、析出した固体を吸引ろ過し、更にTHFで洗浄し、ろ液からTHFを減圧留去した。残渣をシリカゲルカラムクロマトグラフィー（溶離液/クロロホルム→3%メタノール-クロロホルム)により精製し、白色固体として下記のジオール8.90g(17.5mmol,84％)を得た。 After dissolving 10.5 g (20.8 mmol) of the diformyl compound in 120 mL of THF, 3.95 g (83.2 mmol) of lithium aluminum hydride was gradually added and suspended in an ice bath and refluxed overnight. Excess lithium aluminum hydride was decomposed with a saturated aqueous solution of sodium sulfate, and the precipitated solid was suction filtered, further washed with THF, and THF was distilled off from the filtrate under reduced pressure. The residue was purified by silica gel column chromatography (eluent / chloroform → 3% methanol-chloroform) to obtain 8.90 g (17.5 mmol, 84%) of the following diol as a white solid.
上記のジオール0.254g(0.500mmol)にDMF2.5mLを加えて溶解し、得られた溶液に塩化チオニル0.30mL(4.10mmol)を加えた。室温で30分撹拌後、水を加えて吸引ろ過し、肌色固体として下記の塩化物0.214g(0.392mmol,78%)を得た。 To 0.254 g (0.500 mmol) of the above diol, 2.5 mL of DMF was added and dissolved, and 0.30 mL (4.10 mmol) of thionyl chloride was added to the resulting solution. After stirring at room temperature for 30 minutes, water was added and suction filtered to obtain 0.214 g (0.392 mmol, 78%) of the following chloride as a flesh-colored solid.
DMF4.0mLに上記の塩化物0.214g(0.392mmol)、続いてチオ酢酸カリウム0.359g(2.83mmol)を加え、室温で一晩撹拌した。水を加えた後、クロロホルムにより抽出し、溶媒を減圧留去した。残渣をシリカゲルカラムクロマトグラフィー(溶離液/クロロホルム)により精製し、薄茶色固体として下記のチオエステル基含有二官能性クラウンエーテル0.185g(0.294mmol,75%)を得た。 0.214 g (0.392 mmol) of the above chloride was added to 4.0 mL of DMF, followed by 0.359 g (2.83 mmol) of potassium thioacetate, and the mixture was stirred overnight at room temperature. After adding water, the mixture was extracted with chloroform, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent / chloroform) to obtain 0.185 g (0.294 mmol, 75%) of the following thioester group-containing bifunctional crown ether as a light brown solid.
［調製例２］ 一般式(i)で表される化合物の合成
トルエン51.0g(0.550mol)にtert-ブチルクロライド103g(1.10mol)を加え、無水塩化アルミニウム3.04g(0.0230mol)を6時間かけて少しずつ加えた後、室温で24時間撹拌した。これを、冷希硫酸水溶液に加えて、油層を水で洗浄後、飽和炭酸ナトリウム水溶液で洗浄し、無水硫酸マグネシウムで乾燥したのち、溶媒（トルエン）を減圧留去した。残渣を減圧蒸留により精製し、無色オイルとして45.3g(0.222mol)の3,5-ジ-tert-ブチルトルエンを得た。
[Preparation Example 2] Synthesis of compound represented by general formula (i) 103 g (1.10 mol) of tert-butyl chloride was added to 51.0 g (0.550 mol) of toluene, and 3.04 g (0.0230 mol) of anhydrous aluminum chloride was added over 6 hours. Was added little by little, followed by stirring at room temperature for 24 hours. This was added to a cold dilute aqueous sulfuric acid solution, and the oil layer was washed with water, then with a saturated aqueous sodium carbonate solution and dried over anhydrous magnesium sulfate, and then the solvent (toluene) was distilled off under reduced pressure. The residue was purified by distillation under reduced pressure to obtain 45.3 g (0.222 mol) of 3,5-di-tert-butyltoluene as a colorless oil.
3,5-ジ-tert-ブチルトルエン21.8g(107mmol)、ピリジン86mL(1.07mol)に5M KOH水溶液40mLを加えたのち、氷浴下で過マンガン酸カリウム37.1g(235mmo1)を少しずつ加え、一晩還流した。2M硫酸300mLを加え、吸引ろ過し、残渣を水、続いて酢酸エチルで洗浄した。有機層を無水硫酸マグネシウムで乾燥後、溶媒を減圧留去した。残渣をn-ヘキサンで再結晶し、白色固体として3,5-ジ-tert-安息香酸9.83g(41.9mmol,16%)を得た。 After adding 40 mL of 5M KOH aqueous solution to 2,1.8 g (107 mmol) of 3,5-di-tert-butyltoluene and 86 mL (1.07 mol) of pyridine, 37.1 g (235 mmo1) of potassium permanganate was added little by little in an ice bath, Refluxed overnight. 300 mL of 2M sulfuric acid was added and suction filtered, and the residue was washed with water followed by ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from n-hexane to obtain 9.83 g (41.9 mmol, 16%) of 3,5-di-tert-benzoic acid as a white solid.
3,5-ジ-tert-ブチル安息香酸14.41g(18.8mmol)を塩化チオニル10.0mL(137mmol)に加え、50℃で一晩撹拌後、過剰の塩化チオニルを減圧留去した。更にベンゼンを加えて共沸させ、残っている塩化チオニルを除去した。このようにして合成された酸クロリドをTHF20mLに溶解させて得た溶液を、3-アミノ-1-プロパノール4.32g(56.4mmol)をTHF20mLに加えて得た溶液に、氷浴下で少しずつ滴下した。滴下後、室温で2時間撹拌した後、水50mL、3M HCl 100mLを加え、酢酸エチルで抽出した。抽出液を無水硫酸マグネシウムにより乾燥し、溶媒を減圧留去した。残渣を減圧乾燥し、白色固体として下記のアミド5.17g(17.7mmol,94%)を得た。 14.41 g (18.8 mmol) of 3,5-di-tert-butylbenzoic acid was added to 10.0 mL (137 mmol) of thionyl chloride and stirred at 50 ° C. overnight, and then excess thionyl chloride was distilled off under reduced pressure. Further benzene was added for azeotropy to remove the remaining thionyl chloride. A solution obtained by dissolving the acid chloride thus synthesized in 20 mL of THF was added dropwise to a solution obtained by adding 4.32 g (56.4 mmol) of 3-amino-1-propanol to 20 mL of THF in an ice bath little by little. did. After dropping, the mixture was stirred at room temperature for 2 hours, 50 mL of water and 100 mL of 3M HCl were added, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure to obtain 5.17 g (17.7 mmol, 94%) of the following amide as a white solid.
上記のアミド5.17g(17.7mmol)にTHF50mLを加えて溶解させた後、氷浴下で水素化リチウムアルミニウム2.50g(52.8mmol)を加え、一晩還流した。還流後、飽和硫酸ナトリウム水溶液を加え、過剰な水素化リチウムアルミニウムを分解した。これを吸引ろ過し、固体を酢酸エチルにより洗浄し、ろ液から溶媒を減圧留去した。シリカゲルカラムクロマトグラフィー(溶離液/クロロホルム→3%メタノール-クロロホルム)により精製を行い、無色オイルとして4.78g(17.3mmol)のアミン化合物を得た。これにメタノール40mLを加えて溶解させ、氷浴下でlO% HPF6 40mLを撹拌しながら少しずつ加え、析出した白色固体を吸引ろ過した。更に、白色固体に水100mLを加えてろ過し、合わせたろ液を冷却し白色固体を析出させ、吸引ろ過した。この操作を3回繰り返した後、白色固体をアセトニトリルで洗浄・ろ過し、ろ液を無水硫酸マグネシウムにより乾燥させた。ろ液の溶媒を減圧留去し、減圧乾燥後白色固体として下記の化合物7.15g(16.9mmol,95%)を得た。この化合物を一般式(i)で表される化合物として本発明のロタキサンの製造に用いた。 After dissolving 50 mL of THF in 5.17 g (17.7 mmol) of the above amide, 2.50 g (52.8 mmol) of lithium aluminum hydride was added in an ice bath and refluxed overnight. After refluxing, a saturated aqueous sodium sulfate solution was added to decompose excess lithium aluminum hydride. This was suction filtered, the solid was washed with ethyl acetate, and the solvent was distilled off from the filtrate under reduced pressure. Purification was performed by silica gel column chromatography (eluent / chloroform → 3% methanol-chloroform) to obtain 4.78 g (17.3 mmol) of the amine compound as a colorless oil. 40 mL of methanol was added to dissolve this, and 40 mL of 10% HPF 6 was added little by little with stirring in an ice bath, and the precipitated white solid was suction filtered. Further, 100 mL of water was added to the white solid and filtered, and the combined filtrate was cooled to precipitate a white solid and suction filtered. After repeating this operation three times, the white solid was washed and filtered with acetonitrile, and the filtrate was dried over anhydrous magnesium sulfate. The solvent of the filtrate was distilled off under reduced pressure, and after drying under reduced pressure, 7.15 g (16.9 mmol, 95%) of the following compound was obtained as a white solid. This compound was used as a compound represented by the general formula (i) for the production of the rotaxane of the present invention.
［調製例３］ 末端フェニレンジイソシアナート化ポリテトラヒドロフランの合成
無水ポリテトラヒドロフラン0.624g(0.624mmol)にクロロホルム4mLを加えた。この溶液をアルゴン雰囲気下で、m-フェニレンジイソシアナート1.00g(6.24mmol)をクロロホルム10mLに加えることにより得た溶液にゆっくり滴下した。その後、ジラウリン酸ジ-n-ブチルスズ18.9mg(30.0μmol)を加え、室温で1日撹拌し、蒸留により精製し、白色固体として下記の末端フェニレンジイソシアナート化ポリテトラヒドロフランを得た。この化合物を一般式(iii)で表される化合物として本発明のロタキサンの製造に用いた。
[Preparation Example 3] Synthesis of terminal phenylene diisocyanated polytetrahydrofuran 4 mL of chloroform was added to 0.624 g (0.624 mmol) of anhydrous polytetrahydrofuran. This solution was slowly added dropwise to a solution obtained by adding 1.00 g (6.24 mmol) of m-phenylene diisocyanate to 10 mL of chloroform under an argon atmosphere. Thereafter, 18.9 mg (30.0 μmol) of di-n-butyltin dilaurate was added, stirred at room temperature for 1 day, and purified by distillation to obtain the following terminal phenylene diisocyanated polytetrahydrofuran as a white solid. This compound was used as a compound represented by the general formula (iii) for the production of the rotaxane of the present invention.
［実施例１］ ［３］ポリロタキサンの製造
調製例１で得られた二官能性クラウンエーテル430mg(0.684mmol)および調製例２で得られた化合物276mg(0.653mmol)にクロロホルム1.5mLを加えて溶解させた後、調製例３で得られた末端フェニレンジイソシアナート化ポリテトラヒドロフラン386mg(0.311mmol)をクロロホルム0.50mLに溶かして加えた。その後、ジラウリン酸ジ-n-ブチルスズ42mg(60μmol)を加え、室温で1日撹拌した。分取GPCの高分子量体のフラクションを分取し、薄茶色固体として下記の[3]ポリロタキサン838mg(導入率80%)を得た。
[Example 1] [3] Production of polyrotaxane Dissolve 1.5 mL of chloroform in 430 mg (0.684 mmol) of the bifunctional crown ether obtained in Preparation Example 1 and 276 mg (0.653 mmol) of the compound obtained in Preparation Example 2. Then, 386 mg (0.311 mmol) of the terminal phenylene diisocyanated polytetrahydrofuran obtained in Preparation Example 3 was dissolved in 0.50 mL of chloroform and added. Thereafter, 42 mg (60 μmol) of di-n-butyltin dilaurate was added, and the mixture was stirred at room temperature for 1 day. The fraction of the high molecular weight fraction of preparative GPC was fractionated to obtain 838 mg (introduction rate 80%) of the following [3] polyrotaxane as a light brown solid.
上記の[3]ポリロタキサン820mg(0.286mmol)にDMF2.00mLを加えて溶解させ、トリエチルアミン0.29mL(2.10mmol)を加えた。その後、無水酢酸0.180mL(1.80mmol)を加え、一晩撹拌した。撹拌後、2M HCl 30mLを加え、クロロホルムで抽出し、無水硫酸マグネシウムにより乾燥した。その後、溶媒を減圧留去し、分取GPCにより精製し、白色固体として下記のN-アセチル化[3]ポリロタキサン681mgを得た。 To the above [3] polyrotaxane 820 mg (0.286 mmol), 2.00 mL of DMF was added and dissolved, and 0.29 mL (2.10 mmol) of triethylamine was added. Thereafter, 0.180 mL (1.80 mmol) of acetic anhydride was added and stirred overnight. After stirring, 30 mL of 2M HCl was added, extracted with chloroform, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and the residue was purified by preparative GPC to obtain 681 mg of the following N-acetylated [3] polyrotaxane as a white solid.
脱気したメタノール30mLをアルゴン雰囲気下でアセチルクロリド0.509mL(4.50mmol)に加え、溶解した。このメタノール溶液20mLをアルゴン雰囲気下、上記のN-アセチル化[3]ポリロタキサン404mgに加え8時間還流した。溶媒を減圧留去した後、減圧乾燥させ、黄色固体として下記の[3]ポリロタキサン403mgを得た。この[3]ポリロタキサンは４個のチオール基を有し、トポロジカル架橋剤として用いることができる。 30 mL of degassed methanol was added and dissolved in 0.509 mL (4.50 mmol) of acetyl chloride under an argon atmosphere. Under an argon atmosphere, 20 mL of this methanol solution was added to 404 mg of the above N-acetylated [3] polyrotaxane and refluxed for 8 hours. After the solvent was distilled off under reduced pressure, the residue was dried under reduced pressure to obtain 403 mg of the following [3] polyrotaxane as a yellow solid. This [3] polyrotaxane has four thiol groups and can be used as a topological crosslinking agent.
［実施例２］ ポリロタキサンネットワークの合成
チオール基がオレフィン、イソシアナート、チオールなどの様々な基質と容易に反応することが知られている。そこで、実施例１で得られたチオール基含有[3]ポリロタキサンを架橋剤として用いて、ポリロタキサンネットワークの合成を行った。
Example 2 Synthesis of Polyrotaxane Network It is known that thiol groups easily react with various substrates such as olefins, isocyanates, thiols and the like. Therefore, a polyrotaxane network was synthesized using the thiol group-containing [3] polyrotaxane obtained in Example 1 as a crosslinking agent.
該チオール基含有[3]ポリロタキサン65.5mg(0.0222mmol)をクロロホルムO.2mLに溶解させて得た溶液に、下記の末端トリレンジイソシアナート化されたポリブタンジオール1236.Omg(0.0355mmol)を加えた。 To a solution obtained by dissolving 65.5 mg (0.0222 mmol) of the thiol group-containing [3] polyrotaxane in 0.22 mL of chloroform, 1236.Omg (0.0355 mmol) of polybutanediol converted to terminal tolylene diisocyanate was added. It was.
その後、触媒であるジラウリン酸ジ-n-ブチルスズ6.30mg(10.0μmol)を加え、室温で一日撹拌した。その結果、無色透明のゲルが沈殿した。溶媒を減圧留去した後、このゲルを減圧乾燥させて、黄色固体としてポリロタキサンネットワーク100mg(98%)を得た。 Thereafter, 6.30 mg (10.0 μmol) of di-n-butyltin dilaurate as a catalyst was added and stirred at room temperature for one day. As a result, a colorless and transparent gel was precipitated. After the solvent was distilled off under reduced pressure, the gel was dried under reduced pressure to obtain 100 mg (98%) of polyrotaxane network as a yellow solid.
生成したポリロタキサンネットワークは、クロロホルムで膨潤しているときは、もろくて粘性の高い寒天のようであるが、乾燥してくると徐々に固くなり、完全に乾燥すると少し柔軟性のある固体となった。そのゲルのクロロホルムに対する室温での膨潤率は2500％であった。なお、膨潤率は以下の式で表される：膨潤率＝（膨潤時の重量−乾燥時の重量）／（乾燥時の重量）。 The resulting polyrotaxane network appears to be a brittle and viscous agar when swollen with chloroform, but it gradually hardens as it dries and becomes a slightly flexible solid when it dries completely . The swelling rate of the gel with respect to chloroform at room temperature was 2500%. The swelling rate is expressed by the following formula: swelling rate = (weight when swollen−weight when dried) / (weight when dried).
Claims (5)
（式中、Ｒ１は独立に、エンドキャップとして働く一価の基であり、Ｒ２は、下記の式：
で表される二価の基の群から選ばれる直鎖状の二価の基からなる直鎖部である。）
で表される軸成分と、
該軸成分の直鎖部を周回する状態で保持される、少なくとも一個の官能基を有するクラウンエーテル分子少なくとも二個からなる輪成分と、
を有するロタキサンからなる、ロタキサン以外のポリマーの架橋用架橋剤。 General formula R 1 -R 2 -R 1
(Wherein R 1 is independently a monovalent group acting as an end cap, and R 2 is represented by the following formula:
A straight chain portion composed of a straight chain divalent group selected from the group of divalent groups represented by the formula: )
An axial component represented by
A ring component composed of at least two crown ether molecules having at least one functional group, which is held in a state where it circulates around the linear portion of the shaft component;
A cross-linking agent for cross-linking polymers other than rotaxane, comprising rotaxane having
（式中、Ｒ１ 及びＲ ２ は請求項１に記載の通りである。）
で表される軸成分と、
該軸成分の直鎖部を周回する状態で保持される、少なくとも一個の官能基を有するクラウンエーテル分子少なくとも二個からなる輪成分と、
を有するロタキサンにより、該ロタキサンが有する官能基と反応する反応性基を一分子中に少なくとも２個有する、ロタキサン以外のポリマーを架橋させることからなるポリマーの架橋方法。 General formula R 1 -R 2 -R 1
(Wherein R 1 and R 2 are as defined in claim 1 ).
An axial component represented by
A ring component composed of at least two crown ether molecules having at least one functional group, which is held in a state where it circulates around the linear portion of the shaft component;
A method for crosslinking a polymer comprising cross-linking a polymer other than a rotaxane having at least two reactive groups in one molecule that react with a functional group possessed by the rotaxane.
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| US6100329A (en) * | 1998-03-12 | 2000-08-08 | Virginia Tech Intellectual Properties, Inc. | Reversible, mechanically interlocked polymeric networks which self-assemble |
| JPH11302329A (en) * | 1998-04-20 | 1999-11-02 | Jsr Corp | Curable liquid resin composition and its cured product |
| JP3522634B2 (en) * | 2000-03-21 | 2004-04-26 | 住友ベークライト株式会社 | Anisotropic conductive adhesive |
| US6828378B2 (en) * | 2000-04-28 | 2004-12-07 | Center For Advanced Science And Technology Incubation, Ltd. | Compound comprising crosslinked polyrotaxane |
| DE60036029T2 (en) * | 2000-07-03 | 2008-04-30 | Japan Tissue Engineering Co., Ltd., Gamagori | BASIC MATERIALS FOR TISSUE GENERATION, TRANSPLANT MATERIALS AND METHOD FOR THE PRODUCTION OF SELF |
| JP2002080509A (en) * | 2000-09-04 | 2002-03-19 | Sekisui Chem Co Ltd | Maleimide vinyl ether derivative and photocurable resin composition containing the same |
| JP3968414B2 (en) * | 2001-11-02 | 2007-08-29 | 独立行政法人産業技術総合研究所 | Monomers for producing poly [3] rotaxane and methods for producing the same. |
| JP3680133B2 (en) * | 2002-08-27 | 2005-08-10 | 独立行政法人産業技術総合研究所 | Rotaxane complex and method for producing the same. |
| JP4467262B2 (en) * | 2003-08-28 | 2010-05-26 | 株式会社ブリヂストン | Cross-linked body, method for producing the same, and method for recycling the same |
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2004
- 2004-07-16 JP JP2004210336A patent/JP5089015B2/en not_active Expired - Lifetime
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